KR100293041B1 - Polymers with N, N-disubstituted sulfonamide pendant groups and uses thereof - Google Patents

Abstract

The invention is formula R ¹ -SO ₂ -N (CO-OR ² ) -R ³ -O-CO-CR ⁴ = CH ₂ and R ¹ -N (CO-OR ² ) -SO ₂ -R ³ -O Monomer of —CO—CR ⁴ ═CH ₂ , wherein R ¹ is (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl, (C ₆ -C ₁₄ ) aryl or (C ₇ -C ₂₀ Is an aralkyl radical, wherein each methylene group in the alkyl containing radicals is optionally substituted by a hetero atom, and R ² is (C ₃ -C ₁₁ ) alkyl, (C ₃ -C ₁₁ ) alkenyl or (C ₇ -C ₁₁ ) aralkyl, R ³ is unsubstituted or substituted (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₆ -C ₁₄ ) aryl or (C ₇ -C ₂₀ ) an aralkyl radical, R ⁴ is a hydrogen atom or a methyl group.

The invention also relates to the general formula -R ³ -N (CO-OR ² ) -SO ₂ -R ¹ (I) and / or -R ³ -SO ₂ -N (CO-OR ² ) -R ¹ (II) A polymer comprising at least 5 mol% of units having a pendant group, a radiation comprising a compound (a) which forms an acid under the influence of actinic radiation, and an acid decomposable compound having a higher solubility of its decomposition product in an aqueous alkaline developer than the starting compound. A recording material comprising a sensitive compound (b), wherein the acid degradable compound (b) is a polymer of this type, and a support and a radiation sensitive layer.

The mixtures according to the invention are particularly suitable for producing offset printing plates and photoresists.

Description

[Name of invention]

Polymers with N, N-disubstituted sulfonamide pendant groups and uses thereof

Detailed description of the invention

The present invention relates to a monomer containing an N, N-disubstituted sulfonamide group, a polymer containing an N, N-disubstituted sulfonamide pendant group, and a compound that forms an acid under the influence of actinic radiation ( a), a radiation sensitive mixture containing an acid-decomposable compound (b) having a higher solubility of its decomposition product in the aqueous alkaline developer than the starting compound and a polymeric binder (c) that is insoluble in water or water-soluble or at least swellable in alkaline aqueous solutions. (radiation-sensitive mixture).

It is particularly suitable for recording materials comprising a substrate for producing an offset printing plate and a photoresist and a radiation sensitive layer.

Positive radiation sensitive recording layers, i.e. layers in which solubility is much larger in the irradiated zone than in the non-irradiated zone, are known. As the photosensitive component in these layers, especially ortho-naphthoquinonediazide is usually acceptable. However, the photosensitivity of these layers is usually not satisfactory.

So-called relatively "chemically enhanced" mixtures are highly photosensitive because their quantum yield is greater than one. In general, positive "chemically enhanced" mixtures usually contain acid-forming and acid-decomposable components whose solubility of their degradation products in aqueous alkaline developers is much higher than that of the initial compounds.

Acid decomposable compounds used to date include monomeric and polymeric acetals and aromatic compounds as hydroxyl or amino components (see US Patent Application No. 3 779 778) and orthoesters and amide acetals (DE-B 26). 10, 842) containing O, N-acetal. Positive radiation sensitive mixtures include polymeric orthoesters (see EP-B 0 022 571), polymeric aliphatic acetals (Germany Patent No. 27 18 254), enol ethers (EP-B 0 006). 627) and N-acyliminocarbonates (see EP-B 0 006 626). Mixtures of this type for initiating the decomposition reaction require not only photochemically generated acids but also water, which causes problems in practical applications. Moreover, many of these compounds are not readily available.

Positive radiation sensitive mixtures containing a compound which produces an acid upon irradiation and which also contain a polymer having an acid labile t-butoxycarbonyl or t-butoxycarbonyloxy pendant group are described in European Patent Application No. 0 102 450 And EP 0 366 590. However, similar mixtures containing low molecular weight compounds having acid labile groups instead of the above polymers are described in EP 0 249 139. Generally, as an acid labile group in a low molecular weight compound whose molecular weight is less than 1,000, t-butoxy, t-butoxycarbonyl, t-butoxycarbonyloxy, 1-methyl-1-phenylethoxycarbonyl And trimethylsilanyloxy groups. On the other hand, the above system does not require water to initiate the decomposition reaction but has other disadvantages. For example, they exhibit a relatively high "dark ablation" (eg, the solubility of the radiation sensitive layer in the developer is relatively high even in the unexposed areas), so that the difference between the exposed and non-exposed areas is small.

It is an object of the present invention, in particular to positive, "chemically enhanced" mixtures which are simple and inexpensive and which are sensitive to actinic radiation, in particular excimer lasers and actinic radiation emitted by high-pressure mercury lamps. It is an attempt to develop suitable acid degradable compounds.

The object is that according to the invention, a monomer having a N, N-disubstituted sulfonamide group of the following general formula (I) or (II) and a unit having a pendant group of the general formula (I) and / or (II) By providing a polymer that is at least mole%.

-R ³ -N (CO-OR ² ) -SO ₂ -R ¹ (Ⅰ)

-R ³ -SO ₂ -N (CO-OR ² ) -R ¹ (II)

In the above formula,

R ¹ is (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl, (C ₆ -C ₁₄ ) aryl or (C ₇ -C ₂₀ ) aralkylradical, wherein in a radical containing alkyl Each methylene group is unsubstituted or substituted with a hetero atom),

R ² is a (C ₃ -C ₁₁ ) alkyl, (C ₃ -C ₁₁ ) alkenyl or (C ₇ -C ₁₁ ) aralkyl radical,

R ³ is an unsubstituted or substituted (C ₁ -C ₁₂ ) alkylene, (C ₃ -C ₁₂ ) cycloalkylene, (C ₆ -C ₁₅ ) arylene or (C ₈ -C ₂₀ ) arylenedialkyl radical to be.

R ² is preferably a (C ₃ -C ₆ ) alkyl radical, particularly preferably an isopropyl, secondary-butyl or tert-butyl radical.

As described in the examples, the polymer contains units having the general formula (I) or (II) groups, preferably from 10 to 90 mol%, particularly preferably from 20 to 80 mol%. Therefore, copolymers are usually preferred over homopolymers. The molecular weight of the polymer is usually 2,000 to 100,000, preferably 5,000 to 50,000.

Suitable comonomers are in principle all polymerizable compounds free of acid degradable groups. By "non acid cleavable" is meant herein that the group cannot be decomposed by the acid produced in the mixture according to the invention. The comonomers are for example acrylic acid, methacrylic acid, (C ₁ -C ₁₀ ) alkyl acrylates and methacrylates, (C ₆ -C ₁₀ ) aryl acrylates and methacrylates (especially phenyl acrylates, Phenyl methacrylate and pyrocatechol monomethacrylate), acrylamide, methacrylamide, unsubstituted or substituted N- (C ₁ -C ₁₀ ) alkylacrylamide and -methacrylamide (especially N- (2 -hydroxyethyl) acrylamide and-methacrylamide), N, N- di - (C ₁ -C ₁₀₎ alkyl acrylamide, N- phenyl-acrylamide and-methacrylamide, N, N- diphenyl-acrylamide And -methacrylamide, N- (C ₁ -C ₁₀ ) alkyl-N- (C ₆ -C ₁₀ ) arylacrylamides (especially N-phenyl-N-methylacrylamide and -methacrylamide), N-phthal Imidomethyl-methacrylamide, allyl compounds such as allyl esters and allyl oxyethanol, vinyl compounds such as vinyl ethers and vinyl s Tere), vinyl aromatic compounds (e.g., styrene, alkylstyrene, alkoxystyrene, hydroxystyrene, alkyl-hydroxystyrene, acetoxystyrene, α-methylstyrene, α-methyl-hydroxystyrene) and finally acrylonitrile And methacrylonitrile. It is convenient under certain circumstances to use comonomers which are less preferred than these but have acid decomposable groups.

Preferred monomers having an N, N-disubstituted sulfonamide group of formula (I) are R ¹ -SO ₂ -N (CO-OR ² ) -R ³ -O-CO-CR ⁴ = CH _2, wherein Preferred monomers having a group of II) are R ¹ -N (CO-OR ² ) -SO ₂ -R ³ -O-CO-CR ⁴ = CH ₂ , where R ⁴ is a hydrogen atom or a methyl group. Preferred monomers are therefore acrylates or methacrylates.

Monomers having an N, N-disubstituted sulfonamide group are reacted with an activated carboxylic acid ester containing a group -OR ² as an alcohol component in the presence of a catalytic amount of an organic base (e.g. 4-dimethylaminopyridine). It can be prepared from the corresponding compound having a monocyclic sulfonamide group.

N-monosubstituted sulfonamides can be prepared from sulfonic acids and primary amines according to methods known to those skilled in the art. The method for producing a monomer having a group of general formula (II) generally uses monoamine. Monoamines are preferably straight or branched chain alkylamines having 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms [eg methylamine, ethylamine, propylamine, isopropylamine, butylamine, secondary- Butylamine, isobutylamine, t-butylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine and hexylamine]. Furthermore, cycloalkylamines having 3 to 12 carbon atoms are preferred, and cycloalkylamines having 5 to 8 carbon atoms such as cyclopentylamine, cyclohexylamine, cycloheptylamine and cyclooctylamine are particularly preferred. Among the aromatic monoamines, those having 6 to 15 carbon atoms are preferred, and the aromatic moiety thereof may be particularly substituted with halogen atoms, alkyl or alkoxy groups. Examples of preferred aromatic amines include aniline, 4-methylaniline, 4-ethylaniline, 4-methoxyaniline, 3-methoxyaniline, 4-ethoxyaniline, 4-phenoxyaniline, naphthylamine, biphenylamine, 1- and 2-aminoanthracene and 9-aminophenanthrene. In aralkylamine, it is preferable that it is C7-20. These may be substituted in the same way as aromatic amines. Examples of suitable aralkylamines are benzylamine, 4-methoxybenzylamine, 2,2- and 3,3-diphenylpropylamine.

In preparing a monomer having a group of general formula (I), a primary amine having a polymerizable olefin-based unsaturated group or a functional group bonded to the polymerizable group is used. Hydroxyamines such as ethanolamine are particularly suitable for preparing the above acrylates and methacrylates. The hydroxy group can be reacted with, for example, methacrylic anhydride to introduce a polymerizable double bond.

The same applies to the sulfonic acids used in the preparation of monomers for amines. Preferred sulfonic acids for preparing monomers having a group of general formula (I) include methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid Hexanesulfonic acid, perfluorooctanesulfonic acid, benzenesulfonic acid, pentafluorobenzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid. Thus, to prepare monomers having a group of formula (II), sulfonic acids functionalized in the same way as amines for preparing monomers having a group of formula (I) are used. An example of a functionalized sulfonic acid is 4-hydroxy benzenesulfonic acid.

Sulphonic acid is generally not used in the reaction as described above, but in the more reactive, so-called "activated" form. This includes in particular sulfonyl halides, in particular sulfonyl chloride.

So-called "activated carboxylic acid esters" are those capable of carrying out acylation of -CO-OR ² and N-monosubstituted sulfonamides. These are especially dialkyldicarbonates (= pyrocarboxylic acid dialkyl esters). Particular preference is given to di-tert-butyl dicarbonate (= O [CO ₂ -C (CH ₃ ) ₃ ] ₂ ).

The reaction of the activated carboxylic acid ester with the N-monosubstituted sulfonamide is, under reaction conditions, in each case from 0.01 to 10 mole percent, preferably 0.05 to 2 mole, based on the molar amount of the N-monosubstituted sulfonamide It is preferably carried out in a solvent which does not initiate any irreversible reaction with the other components in the reaction mixture in the presence of% organic base. The base is preferably a tertiary amine such as dialkylaminopyridine. Suitable solvents are in particular tetrahydrofuran, ethyl acetate, diethyl ether, butanone (= methyl ethyl ketone). It was found to be convenient to introduce N-monosubstituted sulfonamides and organic bases in dissolved form as an initial charge and to slowly add activated carboxylic acid esters to this mixture. The reaction is generally carried out at a temperature of 0 to 80 ° C, preferably 10 to 50 ° C. The reaction product can be separated into sufficient purity by pouring the reaction mixture into water, filtering the precipitate and drying, or simply stripping the volatile components under reduced pressure. If necessary, it can be further purified by recrystallization, reprecipitation, distillation or preparative chromatography.

According to the present invention, an acid-decomposable compound (b) having a solubility of an acid-forming compound (a) and its decomposition product in an aqueous alkaline developer under the influence of actinic radiation than that of the starting compound, wherein the acid-decomposable compound (b ) Is a polymer containing 5 mol% or more of units having N, N-disubstituted sulfonamide pendant groups of general formula (I) or (II).

Under the influence of actinic radiation, suitable as compounds (a), which preferably form strong acids, are, for example, in particular diazonium, phosphonium, sulfonium and iodonium forms, halogen compounds, o-quinone diazidesulfochloride, Esters and amides, and also organometallic / organic halogen mixtures. The above diazonium, phosphonium, sulfonium and iodonium compounds are usually used in the form of their soluble salts in organic solvents, in particular in the form of sulfonates, in particular trifluoromethanesulfonate, tetrafluoro Used in the form of roborate, hexafluorophosphate, hexafluoroantimonate or hexafluoroarsenate. However, halides, esters and amides of 1,2-naphthoquinone-2-diazidesulfonic acid can also be used. However, the acidity of the indene carboxylic acid produced by the irradiation of O-naphthoquinone diazide only corresponds to sufficient imaging differentiation. Thus, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride is preferred in this group, which forms three acids upon irradiation to obtain a relatively large enhancer. Finally, suitable acid formers also include organic halogen compounds, for example compounds containing one or more halogen atoms on carbon atoms or aromatic rings. The spectral sensitivity of the halogen containing compound can be modified and increased by photosensitizers known per se. Examples of particularly suitable acid formers include the above-mentioned compounds as well as 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride; 4-dipropylaminobenzenediazonium tetrafluoroborate, hexafluorophosphate and trifluoromethanesulfonate; 2,5-diethoxy-4-p-tolylmercaptobenzenediazonium tetrafluoroborate, hexafluorophosphate and trifluoromethanesulfonate; 4-anilinobenzenediazonium sulfate and 4-diethylaminobenzenediazonium trifluoromethanesulfonate. Also 4-methyl-6-trichloromethyl-2-pyrone; 4- (3,4,5-trimethoxystyryl) -6-trichloromethyl-2-pyrone; 4- (4-methoxystyryl) -6- (3,3,3-trichloropropenyl) -2-pyrone; 2-trichloromethylbenzimidazole; 2-tribromomethylquinolin-4-one; 2,4-dimethyl-1-tribromoacetylbenzene; 3-nitro-1-tribromoacetylbenzene; 4-dibromoacetylbenzoic acid; 1,4-bis-dibromomethyl-benzene; Substituted 4,6-bis-trichloromethylsecondary-triazines such as 2- (6-methoxynaphthalen-2-yl)-, 2- (naphthalen-1-yl)-, 2- (naphthalene 2-yl)-, 2- [4- (2-ethoxyethyl) -naphthalen-1-yl]-, 2-benzopyran-3-yl, 2-phenanthrene-9-yl-, and 2- (4-methoxyanthracen-1-yl) -4,6-bis-trichloromethyl-secondary-triazine and tris-dibromomethyl-secondary-triazine can also be used.

The proportion of acid forming compound (s) (a) in the mixture varies depending on the composition of the mixture. In each case, good results are obtained at about 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the total weight of solids in the mixture. In particular, in the radiation layer having a thickness of 10 µm or more, it is preferable to use a relatively small amount of an acid forming agent.

The proportion of conventional acid degradable polymers (b) is in each case about 30 to 98% by weight, preferably 50 to 95% by weight, based on the total solids weight in the mixture.

In addition to the acid decomposable compounds according to the invention, other components may be present in the mixture. In particular, there are polymers having t-butoxy carbonyl groups. However, mixtures with additional acid decomposable compounds are usually undesirable.

If necessary, the mixture may further contain a polymeric organic binder. Particularly suitable polymeric binders are phenolic resins, in particular cresol-formaldehyde novolac (novolak, melting point according to DIN 53181: 105 to 120 ° C) and phenol-formaldehyde novolak (melting point according to DIN 53181: 110 to 120 ° C). .

The type and proportion of binder depends on the purpose of the application. The proportion of binder is in each case preferably 5 to 70% by weight, particularly preferably 20 to 50% by weight, based on the total solids weight in the mixture.

Binders that increase alkali solubility by the action of acids can also be used in the mixtures according to the invention. The binder may be, for example, polyhydroxystyrene in which a phenolic OH group is provided with an acid labile group that reduces alkali solubility. The compounds according to the invention clearly reduce the rate of cancer fusion without adversely affecting the photosensitivity of the mixture.

Maleic anhydride and styrene as well as other alkali soluble resins such as copolymers made from methacrylic acid and methyl methacrylate, vinyl acetate and crotonic acid are also suitable as binders.

In addition, a number of resins, preferably vinyl polymers, such as poly (vinyl acetate), polyacrylates, poly (vinyl ethers) and poly (vinylpyrrolidone), which can be modified at the same time by copolymers in turn, can be used. have. The most advantageous ratio of these resins depends on the application requirements and the effects of the development conditions. Typically it is up to 50% by weight based on the total weight of solids in the mixture.

To meet special needs such as flexibility, adhesion or gloss, the radiation sensitive mixture may additionally contain materials such as polyglycol, cellulose derivatives such as ethyl cellulose, wetting agents, dyes and finely divided pigments. Dyes known to be particularly useful are in particular triphenylmethane dyes in the form of carbinol base. The most advantageous quantitative component ratios can be easily found by experiments for each specific case.

Finally, the invention also relates to a recording material comprising a substrate and a radiation sensitive layer containing a mixture according to the invention. The recording material is usually prepared by coating the substrate with a mixture solution.

Suitable solvents for the radiation sensitive mixtures according to the invention include ketones (e.g. methyl ethyl ketone), chlorinated hydrocarbons (e.g. trichloroethylene and 1,1,1-trichloroethane), alcohols (e.g. n-propanol), Ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monoethyl ether and esters such as butyl acetate. It is furthermore possible to use mixtures which may further contain solvents such as acetonitrile, dioxane or dimethylformamide for special purposes. In principle, it is possible to use all solvents which do not irreversibly react with the components of the layer. However, they must be selected according to the intended coating process, the thickness of the layer and the drying apparatus. Preferably a thin layer of about 5 μm or less is applied by spin coating in an experimental amount. A single application to a rotating disk or a medical knife can be used to obtain a layer having a thickness of at least 60 μm with a solution having a solids content of about 40% or less. Both coatings are preferably carried out by immersion coatings, where rapid surface drying is advantageous and is achieved using low boiling solvents. The coating solution is sprayed using a sheet die or applied using a roller to coat the strip-like base material. Each plate (eg zinc plate and multiple metal plate) can be coated by curtain coating.

When compared to other positive layers, in particular o-naphthoquinone diazide, the photosensitivity of the mixtures according to the invention can be made thicker, since the change in thickness is relatively small. It is possible to expose and process a layer having a thickness of 100 μm or more.

Preferred substrates for layers having a thickness of at least 10 μm are plastic sheets which subsequently serve as temporary substrates for the transfer layer. In the case of the above object and color sheet, for example, a polyester sheet made from polyethylene terephthalate is preferable. However, polyolefin sheets such as polypropylene are also suitable. If the thickness of the layer is less than 10 μm, the thin film substrate used is usually metal. Offset printing plates can be made using any anodized aluminum that can be mechanically, electrochemically coarse and chemically pretreated (eg using polyvinylphosphonic acid, silicate or phosphate). Also suitable as a top layer is a multiple metal plate containing Cu / Cr or brass / Cr. In order to produce letterpress printing plates, the layers produced from the mixtures according to the invention can be applied to zinc or magnesium plates or to microcrystalline alloys which are commercially available for powder-free corrosion, and also to corrosive plastics such as polyoxymethylene Can also be applied. The layers have good adhesion and corrosion resistance on copper or nickel surfaces and are therefore suitable for rotogravure or halftone forme. Similarly, they can be used as photoresist and also for chemical milling.

Thus, for example, a printed circuit board material comprising an insulating plate which is directly coated or optionally coated with copper on one or both sides of the glass or ceramic material which can be pretreated to facilitate adhesion from a temporary substrate, for example. The coating may be carried out by transferring the dry layer to a silicon wafer on the surface, which may suitably be present as a nitride or oxide layer. It is also possible to coat the surfaces, fabrics and wood of wood, fibers and various materials, which are preferably shown by projection and resistant to the effects of alkaline developer.

The coating can be dried using conventional equipment under conventional conditions. It is well tolerated at temperatures of about 100 ° C. and at high temperatures of about 120 ° C. in the short term without the loss of radiation sensitivity continuously observed.

Irradiation may be carried out by conventional radiation sources such as tubular lamps, pulsed xenon discharge lamps, metal halide-doped high-pressure mercury vapor lamps and carbon arcs. arc) lamp]. It is also possible to irradiate with a conventional projection and expansion device under the light of the metal filament lamp, or by contact exposure using a conventional light bulb. Irradiation may also be performed using coherent light of the laser. High power short wavelength lasers are suitable for this purpose, such as argon ion lasers, krypton ion lasers, dye lasers, helium-cadmium lasers and excimer lasers emitting wavelengths from 193 to 633 nm. The laser typically passes over the recording layer under computer control in a manner similar to raster or stroke and illuminates the image behind it in that method.

Irradiation with an electron beam creates additional illustration possibilities. The electron beam, like many other organic materials, can completely decompose and crosslink the mixture according to the present invention, creating a negative image when the unirradiated areas are removed by solvent or exposure without patterning and development. When the intensity of the electron beam is low and / or its recording speed is high, on the contrary, the electron beam shows a different effect in terms of high solubility, that is, the irradiation layer portion can be removed by the developer. The most preferred conditions selected can be readily determined by experiment.

In some cases, after exposure or irradiation of an imaging method, the layer may be removed after the second heat treatment using a commercially identical developer to the commercially available naphthoquinonediazide layer and the photoresist, and the radiation conditions thereof One novel layer can be advantageously adjusted by conventional methods such as developer and planned spray developing equipment. The aqueous developing solution may contain, for example, small amounts of organic solvents as well as alkali metal phosphates, silicates or hydroxides and wetting agents. In certain cases, an organic solvent containing water or a mixture of organic solvents may be used as the developer instead of the aqueous alkaline developer. However, preferred developer is an alkaline aqueous solution.

The most advantageous developer can in some cases be determined by experimentation with layers. In some cases, development can be helped mechanically. The developing plate can be heated to an elevated temperature for a short time in order to enhance the strength during printing and the resistance to leach agents, crystals and inks that can be cured by ultraviolet rays.

The following examples provide preferred monomers having N, N-disubstituted sulfonamide groups according to the invention, polymers prepared using them and preferred photosensitive mixtures prepared using the polymers, which are intended to limit the invention. no. In the examples ppw represents parts by weight.

[Production of Monomer]

1.N-tert-butoxycarbonyl-N- (2-methacryloyloxyethyl) -p-toluenesulfonamide

a) 100 g of p-toluenesulfonyl chloride is slowly added to 80 ml of ethanolamine for 1.5 hours while cooling with ice. The reaction mixture is heated to 120 ° C. and then held at this temperature for 3 hours. After cooling to 70 ° C., a mixture of 60 mL concentrated hydrochloric acid and 300 mL water is added. It is stirred for 10 minutes, then 300 ml of methylene chloride are added, the organic phase is separated and then dried over MgSO ₄ . After stripping the solvent on a rotary evaporator, 111.6 g of a pale yellow solid [N- (2-hydroxyethyl) -p-toluenesulfonamide] is obtained. This product can be used in the next step without further purification.

b) 6.8 ml of methacrylic anhydride and 6.3 ml of triethylamine are added dropwise to a solution of 8.9 g of N- (2-hydroxyethyl) p-toluenesulfonamide in 50 ml of butanone while cooling with ice. Allow the reaction mixture to reach room temperature and then reflux for 4 hours. After cooling it is added ethyl acetate and the mixture is washed with water, the organic phase is separated and dried over magnesium sulfate. After stripping the solvent on a rotary evaporator, 11.2 g of oil [N- (2-methacryloyloxyethyl) -p-toluenesulfonamide] remains. The oily product can be used directly in the next step.

c) 11.8 g of crude N- (2-methacryloyloxyethyl) -p-toluenesulfonamide obtained in the previous step is dissolved in 50 ml of ethyl acetate. While stirring this, 10 mg of 4-dimethylaminopyridine is first added at room temperature, followed by 9.2 g of di-tert-butyl dicarbonate (pyrocarboxylic acid di-tert-butyl ester). After the reaction is complete, the reaction mixture is washed with 10% aqueous NaOH solution. The organic phase is then separated and dried over MgSO ₄ . 14 g of light oil [N-tert-butoxycarbonyl-N- (2-methacryloyloxyethyl) -p-toluenesulfonamide] remain after stripping the solvent on a rotary evaporator.

¹ H-NMR spectrum (60 MHz, CDCl ₃ as solvent; chemical shift in ppm on the δ scale: number of protons in parentheses): 1.3 [9H], 1.95 [3H], 2.45 [3H], 4.0 -4.6 [4H], 5.55 [1H], 6.15 [1H], 7.15-7.4 [2H], 7.65-7.95 [2H].

2.N-tert-butoxycarbonyl-4-methacryloyloxy-N-phenylbenzenesulfonamide

a) Dissolve 200 g of Na salt of 4-hydroxybenzenesulfonic acid in 500 ml of 2N aqueous NaOH, then dilute with 200 ml of water and add 120 g of ethylchloroformate dropwise with stirring at room temperature. The mixture is left overnight and then the precipitate formed (87 g) is filtered off with suction. Stripping of the solvent under reduced pressure and recrystallization from ethanol yields further 129 g of Na salt (white solid) of 4-ethoxycarbonyloxybenzenesulfonic acid. The total yield is 216 g (92% of theory).

b) 95 g of the Na salt of the well-dried 4-ethoxycarbonyloxybenzenesulfonic acid obtained in a) are mixed well with 95 g of PCl ₅ and the reaction mixture is liquefied and heated in the process. Heat for an additional 2 hours in an oil bath (bath temperature: 115 ° C.) and leave at room temperature overnight, then pour into ice and suction filter the sulfonyl chloride. After washing with a large amount of cooling water and drying under reduced pressure, 88 g (94% of theory) of 4-ethoxycarbonyloxybenzenesulfonyl chloride (white solid having a melting point of 71 to 72 DEG C) are obtained.

c) While stirring, 340 ml of aniline was added little by little with 84 g of 4-ethoxycarbonyloxybenzenesulfonyl chloride prepared in b). The mixture is heated at 55 ° C. for 4 h, cooled to rt and poured into 1.7 l of semiconcentrated hydrochloric acid. It is left overnight and then the aqueous phase is filtered off. For the purpose of complete removal of the protecting group, the residue is dissolved in 1.7 L of 2N NaOH aqueous solution and the undissolved material is separated and acidified with HCl to precipitate the product. This was filtered by suction, washed with water and dried to give 54.5 g (70% of theory) of 4-hydroxybenzenesulfanylide (white solid with melting point of 140 ° C).

d) 50 g of 4-hydroxybenzenesulfanide prepared in c) was dissolved in 300 ml of acetone, and 35.6 g of methacrylic anhydride was added, and triethylamine 22.2 was maintained at a temperature not higher than 10 DEG C while cooling and stirring. add dropwise g The temperature of the reaction solution is allowed to reach room temperature and added dropwise to 3 L of H ₂ O with vigorous stirring. After suction filtration and drying, 61 g (yield: 96%) of 4-methacryloyloxybenzenesulfanide (white solid having a melting point of 102 to 103 ° C.) was obtained.

e) 50 g of 4-methacryloyloxybenzenesulfanide prepared in d) was dissolved in 300 ml of acetone, 1 g of 4-dimethylaminopyridine was added, and di-tert-butyldicarbonate in 100 ml of acetone was stirred. 38 g of solution is added dropwise. Stirring is continued for 4 hours at room temperature and precipitated in H ₂ O. After suction filtration and drying, 59 g (90%) of N-tert-butoxycarbonyl-4-methacryloyloxy-N-phenylbenzenesulfonamide (white solid having a melting point of 112 to 114 DEG C) was obtained. do.

NMR spectrum (60 MHz, CDCl ₃ ): 1.3 ppm (9H), 2.1 (3H); 5.8 (1 H), 6.4 (1 H); 7.2-7.6 (7H); 8.0-8.2 (2H)

[Examples 1 to 20]

The homopolymerization of compounds 1 and 2 and the copolymerization with various comonomers (eg pyrocatechol monomethacrylate (PMA) or styrene) are carried out according to methods known in the literature. Table 1 contains a selection of polymers synthesized using Compound 1 and Compound 2 (amounts specified in mole percent).

[Examples 21 to 26]

These embodiments illustrate the manufacturing and processing of the recording material according to the present invention.

Solution containing 9.00 ppw of binder according to Table 1, 0.5 ppp of 4-p-tolylmercapto-2,5-diethoxybenzenediazonium hexafluorophosphate, 0.08 ppw of crystal violet base and 175 ppw of methyl ethyl ketone Spin-coating the electrically activated and anodized aluminum plate and heating at 100 ° C. in a drying oven to form a layer having a thickness of 1.9 μm. The plate is exposed under a 5 KW metal halide lamp at a distance of 110 cm through a halftone step wedge with a density gradient of 0.15 and heated at 100 ° C. for 1 minute, followed by meta It is developed for 30 seconds in an aqueous alkaline developer having a composition of sodium silicate 9H ₂ O 5.5ppw, trisodium phosphate 12H ₂ O 3.4ppw, anhydrous monosodium phosphate 0.4ppw and deionized water 90.7ppw.

In all cases, positive images are obtained from photographers. Table 2 shows that exposure time step 4 of the halftone step wedge is regenerated by being fully open on the printing plate.

* Positive standard printing plate Ozasol ( ^(R) Ozasol) P61 (Hoechst AG)

Example 27

This example shows the suitability of a polymer containing N, N-disubstituted sulfonamide groups for use in positive offset printing plates.

9.00 ppw terpolymer according to Example 19 of Table 1, 4-p-tolyl mercapto-2,5-diethoxybenzenediazonium hexafluorophosphate 0.50 ppw, crystal violet base 0.08 ppw and methyl ethyl ketone The electrically activated and anodized aluminum plate using a solution containing 175 ppw was spin coated and heated at 100 ° C. in a drying oven to form a 1.9 μm thick layer. The plate was exposed for 20 seconds under a 5 KW metal halide lamp at a distance of 110 cm through a half-stage netting step wedge with a density gradient of 0.15, heated at 100 ° C. for 1 minute, and then the aqueous alkaline developer (composition was Development in 30 seconds). The positive print form thus obtained produces more than 170,000 high quality prints in an offset press.

Claims (9)

Compound of general formula (I ') or (II'). R ¹ -SO ₂ -N (CO-OR ² ) -R ³ -O-CO-CR ⁴ = CH ₂ (I ') R ¹ -N (CO-OR ² ) -SO ₂ -R ³ -O-CO-CR ⁴ = CH ₂ (II ') In general formula (I '), R ¹ is methyl, trifluoromethyl, ethyl, propyl, perfluoropropyl, perfluorobutyl, hexyl, perfluorooctyl, phenyl, pentafluorophenyl, p-tolyl or naphthyl, R ³ is unsubstituted or substituted (C ₁ -C ₆ ) alkylene, (C ₅ -C ₆ ) cycloalkylene, (C ₆ -C ₁₂ ) arylene, benzylene or diphenylpropylene, In general formula (II ') R ¹ is (C ₁ -C ₁₂ ) alkyl, (C ₅ -C ₈ ) cycloalkyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl , 4-phenoxyphenyl, naphthyl, biphenyl, benzyl, 4-methoxybenzyl, 2,2- or 3,3-diphenylpropyl, R ³ is methylene, trifluoromethylene, ethylene, propylene, perfluoropropylene, perfluorobutylene, hexylene, perfluorooctylene, phenylene, pentafluorophenylene, p-tolylene or naphthylene, R ² is (C ₃ -C ₆ ) alkyl, R ⁴ is a hydrogen atom or a methyl group. A polymer containing 5 mol% or more of units having pendant groups of the general formulas (I), (II), or (I) and (II). -R ³ -N (CO-OR ² ) -SO ₂ -R ¹ (Ⅰ) -R ³ -SO ₂ -N (CO-OR ² ) -R ¹ (II) In the above formula, in general formula (I), R ¹ is methyl, trifluoromethyl, ethyl, propyl, perfluoropropyl, perfluorobutyl, hexyl, perfluorooctyl, phenyl, pentafluorophenyl, p-tolyl or naphthyl, R ³ is unsubstituted or substituted (C ₁ -C ₆ ) alkylene, (C ₅ -C ₆ ) cycloalkylene, (C ₆ -C ₁₂ ) arylene, benzylene or diphenylpropylene, In general formula (II) R ¹ is (C ₁ -C ₁₂ ) alkyl, (C ₅ -C ₈ ) cycloalkyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl , 4-phenoxyphenyl, naphthyl, biphenyl, benzyl, 4-methoxybenzyl, 2,2- or 3,3-diphenylpropyl, R ³ is methylene, trifluoromethylene, ethylene, propylene, perfluoropropylene, perfluorobutylene, hexylene, perfluorooctylene, phenylene, pentafluorophenylene, p-tolylene or naphthylene, R ² is (C ₃ -C ₆ ) alkyl. The polymer of claim 2 wherein the radical R ² is an isopropyl, secondary-butyl or tert-butyl radical. Compound (a) which forms an acid under the influence of actinic rays and an acid-decomposable compound (b) having a higher solubility of the decomposition product in the aqueous alkaline developing solution than the starting compound, wherein the acid-decomposable compound (b) is used in claim 2 or 3 Radiation-sensitive mixtures. The radiation sensitive mixture according to claim 4, wherein the proportion of acid forming compound (a) is in each case 0.1 to 20% by weight, based on the total weight of solids in the mixture. The radiation sensitive mixture according to claim 4, wherein the proportion of acid decomposable compound (b) is in each case 30 to 98% by weight, based on the total weight of solids in the mixture. The radiation sensitive mixture of claim 4, further comprising an organic polymeric binder. 8. A radiation sensitive mixture according to claim 7, wherein the proportion of polymeric binder is in each case 5 to 70% by weight, based on the total weight of solids in the mixture. A recording material comprising a support and a radiation sensitive layer comprising a radiation sensitive mixture according to any one of claims 4 to 8.